Supporting Information for

Transcription

1 Supporting Information for Triarylamine substituted arylene bisimides as solution processable organic semiconductors for field effect transistors. Effect of substituent position on their spectroscopic, electrochemical, structural and electrical transport properties Adam Pron, *, Renji R. Reghu, Renata Rybakiewicz, Hubert Cybulski, David Djurado, Juozas V. Grazulevicius, **, Malgorzata Zagorska, ***, Irena Kulszewicz-Bajer, Jean-Marie Verilhac IAC/SPrAM (UMR 5819, CEA-CRS-Univ. J. Fourier-Grenoble 1) Laboratoire d Electronique Moleculaire rganique et Hybride, CEA Grenoble, 17 Rue des Martyrs, Grenoble, France Department of rganic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254, Kaunas, Lithuania. Faculty of Chemistry, Warsaw University of Technology, oakowskiego 3, Warszawa, Poland Department of Physical Chemistry and Center for Research in Biological Chemistry and Molecular Materials, University of Santiago de Compostela, Santiago de Compostela, Spain CEA/LITE/LCI, Grenoble, France * adam.pron@cea.fr ** juozas.grazulevicius@ktu.lt *** zagorska@ch.pw.edu.pl 1

2 1. Synthetic procedures Unless specified, chemicals and reagents were purchased from Aldrich and used as received.,-di(4-butylphenyl)-1,4-phenylenediamine was prepared using the reaction sequence depicted in Scheme S1. SCHEME S1 Br H 2 molecular sieves 5 A, toluene, 120 o C Br H 2 Pd(Ac) 2, BIAP, t-a, toluene, 110 o C Br H 1 2 Pd(Ac) 2, t- 3 P, t-a, toluene, 110 o C 3 ammonium formate, Pd/C, methanol, THF, 65 o C H Synthesis of -(diphenylmethylene)-4-bromoaniline (1). Synthetic procedure, described in detail in the literature 1, was followed in the preparation of (1). The product was obtained as yellow crystals (6.29 g, 82.4 % reaction yield) Synthesis of di(4-butylphenyl)amine (2). Palladium acetate ( mg, 0.55 mmol), BIAP (1.02 g, 1.64 mmol) and 5 ml of dry toluene were stirred under argon atmosphere to obtain a palladium- phosphine complex. After 15 minutes, 4-butylaniline (2.73 g, mmol), 4-bromobutylbenzene (4.23 g, mmol), sodium t-butoxide (2.35 g, 27.5 mmol) and toluene (30 ml) were added to the flask and stirred at 110 C for 22 hours under argon. The obtained reaction mixture was first cooled to room temperature and then treated with water (50 ml). In the next step the product was extracted with diethyl ether (10 ml) (three times). Finally the organic phase was dried over anhydrous 2

3 magnesium sulphate for 24 hours. The solvent was removed in a rotary evaporator and the crude product was purified in a chromatographic column (silica gel, methylene chloride/hexane (1/2 + 1 vol % triethylamine), yielding 4.52 g of (2) in a form of yellow oil (88% reaction yield). 1 H MR (CDCl 3, 400 MHz) δ: 7.07 (d, J= 8.4 Hz, 4H), 6.97 (d, J= 8.4 Hz, 4H); 5.4 (s, 1H), 2.55 (t, J= 7.6 Hz, 4H); (m, 4H), (m, 4H), 0,93 (t, J= 7.2 Hz, 6H). Elemental analysis: Calcd for C 20 H 27 1 : C, 85.41, H, 9.61,, Found: C, 85.00, H, 9.30,, 5, Synthesis of -(diphenylmethylene)-, -di(4-butylphenyl)-1,4-phenylenediamine (3). Palladium acetate (95.37 mg, mmol), tri-t-butylphosphine (257.8 mg, mmol) and dry toluene were stirred about 15 minutes under an argon atmosphere to obtain a palladiumphosphine complex. Then -di(phenylmethylene)-4-bromoaniline (4.76 g, mmol), di(4- butylphenyl)amine (3.98 g, mmol) and sodium t-butoxide (1.90 g, mmol) were added to the solution and the reaction mixture was stirred at 110 C for 22 hours under argon. After cooling to room temperature, the product was extracted with diethyl ether, washed with water and then dried over anhydrous magnesium sulphate. ext, the solvent was removed in a rotary evaporator. In the final step the crude product was purified by crystallization with ethyl acetate to yield 6.15 g of (3) (81 % reaction yield). 1 H MR (CDCl 3, 400 MHz) δ: (m, 2H), (m, 3H), (m, 3H), (m, 2H), 7.01 (d, J= 8,4 Hz, 4H), (m, 4H), (m, 2H), (m, 2H), 2.54 (t, J= 7,8 Hz, 4H), (m, 4H), (m, 4H), 0.93 (t, J= 7,4 Hz, 6H). 13 C MR (CDCl 3, 100 MHz) δ: 146.9; 145.6; 143.8; 139.9; 136.8; 136.6; 130.5; 129.6; 129.2; 128.9; 128.5; 128.2; 127.9; 124.1; 123.6; 122.4; 35.0; 33.7; 22.4; Elemental analysis: Calcd for C 39 H 40 2 : C, 87.31, H, 7.46,, Found: C, 86.97, H, 7.46,, Synthesis of,-di(4-butylphenyl)-1,4-phenylenediamine (4). -(diphenylmethylene)-, -di(4-butylphenyl)-1,4-phenylenediamine (4.78 g, 8.92 mmol), ammonium formate (8.43 g, mmol), catalyst (Pd/C, 10%) (1.89 g, mmol), methanol (60 ml) and THF (30 ml) were stirred at 65 C for 4 hours under an argon atmosphere. After cooling to room temperature the solvents were removed in a rotary evaporator. Then the mixture was filtered (silica gel, methylene chloride) to remove the catalyst and concentrated using a rotary evaporator. The crude product was purified by 3

4 chromatography on silica gel (methylene chloride/hexane (2/1 + 1% vol. triethylamine) to yield 3,34 g of (4) in a form of brown oil (96 % reaction yield). 1 H MR (CDCl 3, 400 MHz) δ: 7.00 (d, J=8.4 Hz, 4H), (m, 6H), 6.63 (d, J=8.4 Hz, 2H), 3.56 (s, 2H), 2.56 (t, J= 7.4 Hz, 4H), (m, 4H), (m, 4H), 0.94 (t, J=7.2 Hz, 6H). 13 C MR (CDCl 3, 100 MHz) δ: 146.1; 142.4; 139.5; 135.9; 128.8; 127.3; 122.4; 116.1; 34.9; 33.7; 22.4; FTIR (KBr, cm -1 ): 3446, 3375, 3062, 2957, 2928, 2857, 1621, 1607, 1507, 1324, 1267, 828. UV-vis (CHCl 3 ): λ max = 238 nm, 299 nm. Elemental analysis: Calcd for C 26 H 32 2 : C, 83.87, H, 8.60,, Found: C, 83.52, H, 8.90,, General procedure of the preparation of 1, P1 via condensation reaction between,-di(4-butylphenyl)-1,4-phenylenediamine (4) and the corresponding arylene bisanhydride. The general method of preparing these bisimides can be briefly described as follows. 0.7 g (1.88 mmol) of, -di(4-butylphenyl)-1,4-phenylenediamine (4) and 0.2 g (0.89 mmol) of zinc acetate dihydrate were added to a stirred suspension of 0.89 mmol of: pyromellitic (0.2 g), naphthalene (0.24 g) or perylene (0.35 g) bisanhydride in ml of dry 1-methyl-2- pyrrolidinone (MP). The resulting mixture was stirred at 180 C for 3 hours under argon atmosphere, and then poured into 100 ml of water. The obtained precipitate was filtered off, washed with water and dried in a desiccator. In the next step the crude product was vigorously stirred with 50 ml of acetone for 2 hours. 1 was purified using a chromatographic column (silica gel, and the following eluent: methylene chloride + 1vol% triethylamine). For P1 no chromatographic purification was carried out. The crude product was dissolved in chloroform and precipitated with acetone, while cooling. The obtained solid was filtered off, washed with acetone and dried. The spectroscopic data as well as the elemental analysis of 1 and P1 can be found below., -bis{4-[bis(4-butylphenyl)amino]phenyl}-1,4,5,8-naphthalenetetracarboxylic - 1,4:5,8-bisimide (1). 1 was prepared in a form of a violet solid with the reaction yield of 57%. 1 H MR (CDCl 3, 400 MHz): 8.84 (s, 4H), (m, 24H), 2.59 (t, J= 7.8 Hz, 8H), (m, 8H); (m, 8H), 0,95 (t, J=7.4 Hz, 12H). 13 C MR (CDCl 3, 100 MHz): 163.2; 148.8; 144.9; 138.4; 131.4; ; 128.7; 127.7; 127.1; 127.0; 126.5; 125.3; 121.6; 35.1; 33.7; 22.4; FTIR (KBr, cm -1 ): 3380, 3027, 2956, 2928, 2857, 1716, 1675, 1602, 1581, 1505, 1447, 1346, 1320, 1283, 1247, 1197, 1138, 1118, 981, 855, 829, 769,

5 UV-vis (CHCl 3 ): λ max = 238 nm, 301 nm, 343 nm, 361 nm, 382 nm. Elemental analysis: Calcd for C 66 H : C, 81.15, H, 6.56,, Found: C, 80.74, H, 6.47,, Melting point: 150 o C., -bis{4-[bis(4-butylphenyl)amino]phenyl}-3,4,9,10-perylenetetracarboxylic-3,4:9,10- bisimide (P1). P2 was prepared in a form of a claret solid with the reaction yield of 55%. 1 H MR (CDCl 3, 400 MHz): 8.67 (d, J= 8 Hz, 4 H); 8.53 (d, J= 8 Hz, 4H); 7.22 (m, 24 H); 2.58 (t, J= 7.8 Hz, 8H); (m, 8H); (m, 8H); 0.95 (t, J= 7.4 Hz, 12H). 13 C MR (CDCl 3, 100 MHz): 148.5; 145.0; 138.2; 134.5; 131.5; 129.4; 128.9; 127.2; 126.2; 125.2; 123.5; 123.1; 121.8; 35.1; 33.7; 22.5; FTIR (KBr, cm -1 ): 3444, 2956, 2934, 2853, 1711, 1663, 1597, 1499, 1401, 1351, 1302, 1252, 1175, 1127, 963, 832, 787, 751. UV-vis (CHCl 3 ): λ max =237 nm, 261 nm, 304 nm, 461 nm, 491 nm, 528 nm. Elemental analysis: Calcd for C 76 H : C, 82.86, H, 6.23,, Found: C, 81.58, H, 6.23,, Melting point: 310 o C ,7-Dibromo, -2-ethylhexyl perylene bisimide. Br Br 3,4:9,10-Perylenetetracarboxylic anhydride (1 g, 2.55 mmol) was suspended in 30 ml of concentrated sulfuric acid and 50 mg of iodine was added. It was heated at 80 o C for 45 min followed by drop wise addition of 1.5 ml of bromine for a period of 15 min and stirred for 24 hrs. The reaction mixture was cooled and water was added into it. The precipitated product was filtered, washed with acetone and dried in vacuum. Thus, obtained bromo-substituted perylene dianhydride (0.96 g, 1.74 mmol) suspended in 20 ml of -methylpyrrolidone and mixed with 10 ml of glacial acetic acid. It was heated at 60 o C for 20 min and 2-ethylhexylamine (0.7 ml, 4.36 mmol) was added. The temperature was raised to 120 o C and continued stirring for 12 h under nitrogen atmosphere. The reaction mixture was poured into 200 ml of water and the precipitated product was filtered. It was washed with methanol, subjected to column chromatography (silica gel, eluent: hexane/ethyl acetate, 9:1) and the desired product was isolated. 5

6 1 H MR (300 MHz, CDCl 3 ), δ (ppm): (m, 12H, CH 3 ), (m, 16H, CH 2 ), (m, 2H, CH), (m, 4H, CH 2 ), (d, J = 2.7 Hz, 2H), 8.91 (s, 2H), (d, J = 2.8 Hz, 2H); MS (EI) m/z = 773 (M + ); Yield = 52% ,7-Bis [4-(diphenylamino)phenyl]-, -bis(2-ethylhexyl) perylene bisimide (P2). 1,7-Dibromo-, -2-ethylhexylperylene bisimide (300 mg, 0.39 mmol) and 4- (diphenylamino) phenylboronic acid (250 mg, 0.85 mmol) were dissolved in a solvent mixture of 15 ml of THF and 2 ml of water. Powdered potassium hydroxide (72 mg, 1.28 mmol) was added and the reaction mixture was purged with nitrogen for 10 min. Then the reaction vessel was degassed. Bis(triphenylphosphine)palladium(II) dichloride (8 mg, 0.01 mmol) was added to it and stirred at 80 o C for 8 hrs under nitrogen. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over sodium sulphate and the crude product was purified by column chromatography using silica gel as stationary phase and hexane/ethyl acetate mixture (97:3) as eluent. 1 H MR (300 MHz, CDCl 3 ), δ (ppm): 8.63 (s, 2H), 8.24 (d, J = 2.8 Hz, 2H), 8.06 (d, J = 2.7 Hz, 2H), (m, 12H), (m, 16H), (m, 4H, CH2), (m, 2H, CH), (m, 16H, CH 2 ), (m, 12H, CH 3 ). 13 C MR (75MHz, CDCl 3, δ ppm): 164.1, 148.7, 147.4, 141.0, 135.6, 135.4, 135.3, 132.5, 130.2, 129.8, 129.6, 129.3, 125.4, 124.0, 123.9, 122.3,122.0, 44.5, 38.2, 31.0, 29.0, 24.3, 23.3, 14.4, IR (KBr), υ (cm -1 ): (arene C H) 3061, 3034; (aliphatic C H) 2955, 2924, 2856; (imide C=) 1698; (Ar C=C) 1659, 1586; (imide C ) 1326, Anal. Calc. for C 76 H : C, 82.88; H, 6.22;, 5.09;, 5.81%. Found: C, 82.39, H, 6.44,, 4.85%; MS (MALDI-TF) m/z = ; Yield = 24%. References (1) J. P. Sadighi, R.A. Singer, S.L. chwald, J. Am. Chem. Soc., 120 (1998)

7 2. The results of DFT calculations 1* P1* P2 Figure S1. Structures of 1*, P1* and P2 predicted by DFT calculations. 7

8 Figure S2. Plots of the CAM-B3LYP/6--31G* calculated molecular orbitals of 1*, P1* and P2 contributing to the selected excitation energies. 8

9 TABLE S1: Excitation energies and oscillator strengths for the fifteen lowest singlet-singlet transitions in 1* and P1* (H L indicates a HM LUM transition) 9

10 TABLE S2: Excitation energies and oscillator strengths for the fifteen lowest singlet-singlet transitions in P2 (H L indicates a HM LUM transition) 3. Characteristics of transistors a) b) 10-8 Current (A) =-100V =-80V =-60V =-40V Current (A) =-100V =-80V =-60V =-40V V G (V) V G (V) Figure S3. Transfer characteristics for different negative source and drain voltages ( ), showing unipolar p- channel behaviour for 1 (a) and P1(b). 10

11 10-6 After fabrication Storage under air during 100 days 10-7 Current (A) =-100V =-80V =-60V =-40V =100V =80V =60V =40V V G (V) Figure S4. Transfer characteristics of an ambipolar transistor (4-MTP treatment) made of P2 after fabrication and after 100 days storage under air environment. 11